CN106750358B - A kind of imidazole-2-carboxylic acid's nickel complex, preparation method and applications - Google Patents
A kind of imidazole-2-carboxylic acid's nickel complex, preparation method and applications Download PDFInfo
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Abstract
The invention discloses a kind of imidazole-2-carboxylic acid's nickel complex, preparation method and applications, the molecular formula of imidazole-2-carboxylic acid's nickel complex is C6H6N2Ni0.5O6.The present invention with 2- methylol -1H-4,5- imidazole-2-carboxylic acid as bridging ligand, using hydro-thermal method, by Ni (NO3)2·6H2O and 2- methylol -1H-4,5- imidazole-2-carboxylic acid react, and cooperate ligand with corresponding metal, to obtain new imidazole-2-carboxylic acid's nickel complex.Simply, conveniently, safely, reaction condition is mild, and product is crystal for the synthetic method, and purity is high is studied convenient for consequent activities.The present invention studies the interaction of complex and bovine serum albumin(BSA) (BSA), human serum albumins (HSA) using fluorescent spectrometry.The result shows that stronger interaction can occur for the complex and BSA, HSA, complex can be by blood plasma carrying and storage as drug.
Description
Technical field
The present invention relates to a kind of imidazole-2-carboxylic acid's nickel complexes, preparation method and applications, belong to field of coordinative chemistry.
Background technique
From state university professor B.Rosenbergr of Michigan, United States in 1967 etc. find cis-platinum have anti-tumor activity with
Come, research of the metal complex in terms of biological medicine arouses great concern.Much natural productions containing imidazole ring
Object has a wide range of applications, especially biology, in terms of show very unique performance, such as in antimycotic, anticancer,
And treatment hypoglycemia and physiologic derangement etc. have good application value.Imidazole-2-carboxylic acid's class compound contains multiple match
Position atom, has a variety of coordination modes, complex that can be excellent with various metals forming properties.Nickel is micro member necessary to animal
Element, there are close relationships with animal angiocarpy, endocrine and immune system, and participate in the metabolism of nucleic acid and protein, have
Alleviate the effect that adrenaline increases blood pressure and enhances insulin reduction blood glucose.The synthesis of imidazole-2-carboxylic acid's nickel complex and biology
Activity research has great importance.
Seralbumin is the most abundant albumen in blood plasma, after drug enters the blood circulation of body, not with seralbumin
The hair of drug distribution in vivo, storage, transhipment, metabolism and pharmacological activity is directly affected with the invertibity Non-covalent binding of degree
It waves.Emits stronger Intrinsic fluorescence due to containing amino acid residues such as tryptophan, tyrosine in albumin molecule, drug with it is white
The variation of albumin molecule Intrinsic fluorescence caused by the interaction of albumen can be the knot of fluorescence chromophore in protein molecule
Structure and its locating micro-environmental variation provide useful information.Imidazole-2-carboxylic acid's nickel complex and serum are studied using fluorescent spectrometry
The interaction of albumin, reflection drug property in vivo make us more clearly recognize drug in vivo
Specific effect, the exploitation for the design of drug, screening and new drug provide theoretical foundation.
Summary of the invention
To solve the above-mentioned problems, the object of the present invention is to provide a kind of imidazole-2-carboxylic acid's nickel complex, preparation method and
It is applied.Imidazole-2-carboxylic acid's nickel complex preparation method is simple, and reaction condition is mild, purity is high.Utilize fluorescence spectrum
Method research complex and sero-abluminous interaction find that imidazole-2-carboxylic acid's nickel complex can be with the spontaneous hair of seralbumin
Raw effect, forms that fluorescence is weaker or non-blooming compound and causes BSA, HSA Intrinsic fluorescence between seralbumin
Quenching, and the Binding change of BSA, HSA conformation of protein molecule, binding site is closer to trp residue.
To achieve the goals above, the technical scheme adopted by the invention is that:
A kind of imidazole-2-carboxylic acid's nickel complex of 2- methylol -1H-4,5- imidazole-2-carboxylic acid preparation, the imidazoles dicarboxyl
The molecular formula of sour nickel complex is C6H6N2Ni0.5O6。
A kind of preparation method of imidazole-2-carboxylic acid's nickel complex, comprising the following steps:
(1) it disperses 2- methylol -1H-4,5- imidazole-2-carboxylic acid in solvent, is configured to 2- methylol -1H-4,5- miaow
Azoles dicarboxyl acid concentration is the ligand solution of 0.05mol/L；
By Ni (NO3)2·6H2O is dissolved in solvent, is configured to Ni (NO3)2·6H2O concentration is the nickel salt of 0.05mol/L
Solution；
(2) by nickel salt solution and ligand solution according to 2- methylol -1H-4,5- imidazole-2-carboxylic acid and Ni (NO3)2·6H2O
The ratio of the mass ratio of the material 1:1 mixes；
(3) mixed liquor of step (2) is placed in reaction vessel, reacts 72h, then under the conditions of 110-140 DEG C with 5 DEG C/h
Rate be cooled to room temperature, spontaneously dry to get.
The solvent is deionized water.
The reaction vessel is polytetrafluoroethyllining lining stainless steel cauldron.
Preferably, the reaction temperature is 120 DEG C.
A kind of phase of imidazole-2-carboxylic acid's nickel complex and bovine serum albumin(BSA) (BSA), human serum albumins (HSA)
Interaction.
Application of imidazole-2-carboxylic acid's nickel complex in terms of as research bioactive agents a kind of described in.
Beneficial effects of the present invention:
1, the present invention is coordinated with 2- methylol -1H-4,5- imidazole-2-carboxylic acid for ligand with nickel ion, is obtained a kind of new
Imidazole-2-carboxylic acid's nickel complex, the complex are monoclinic system, P2 (1)/c space group；Cell parameter
α=90 °, β=104.72 (3) °, γ=90 °；V=
817.7A3；Z=4；Dc=1.880Mg/m3；R1=0.0486, ω R2=0.1029.
2, the present invention uses hydro-thermal method, by Ni (NO3)2·6H2O and 2- methylol -1H-4,5- imidazole-2-carboxylic acid carry out anti-
It answers, cooperates ligand with corresponding metal, to obtain new imidazole-2-carboxylic acid's nickel complex.The synthetic method is simple,
Convenient, safety, reaction condition is mild, and product is crystal, and purity is high is studied convenient for consequent activities.
3, the present invention is using fluorescent spectrometry research complex and bovine serum albumin(BSA) (BSA), human serum albumins (HSA)
Interaction.The result shows that stronger interaction can occur for the complex and BSA, HSA, complex can as drug
By blood plasma carrying and storage.
Detailed description of the invention
Fig. 1 is the coordination context diagram of imidazole-2-carboxylic acid's nickel complex.
Fig. 2 is the one-dimensional supermolecule chain structure figure of imidazole-2-carboxylic acid's nickel complex.
Fig. 3 is the Magnetic Properties of Three-Dimensional Supramolecular Complex net structure char of imidazole-2-carboxylic acid's nickel complex.
Fig. 4 is the PXRD map comparison diagram of the simulation and actual measurement of imidazole-2-carboxylic acid's nickel complex.
Fig. 5 is under different temperatures, BSA/HSA solution with imidazole-2-carboxylic acid nickel complex concentration increase fluorescence spectrum
Variation (arrow direction is the increased direction of imidazole-2-carboxylic acid's nickel complex concentration).The fluorescence spectrum of BSA becomes when a is 298K
Change figure, the fluorescence spectrum variation diagram of BSA when b is 308K, the fluorescence spectrum variation diagram of HSA when c is 298K, HSA when d is 308K
Fluorescence spectrum variation diagram；Illustration is fluorescence intensity at 340nm with the increased variation diagram of imidazole-2-carboxylic acid's nickel complex concentration.
Fig. 6 is Stern-volmer curve graph of imidazole-2-carboxylic acid's nickel complex to BSA, HSA under different temperatures.A be with
Object is closed to the Stern-volmer curve graph of BSA, b is Stern-volmer curve graph of the complex to HSA.
Fig. 7 is log-log graph of imidazole-2-carboxylic acid's nickel complex to BSA, HSA under different temperatures.A is complex to BSA
Log-log graph, b is complex to the log-log graph of HSA.
Fig. 8 is under different temperatures, and (arrow is signified for synchronous fluorescent spectrum figure of imidazole-2-carboxylic acid's nickel complex to BSA, HSA
Direction is the increased direction of imidazole-2-carboxylic acid's nickel complex concentration).A, when b, c, d are different temperatures, the synchronous fluorescent spectrum of BSA
Figure；E, when f, g, h are different temperatures, the synchronous fluorescent spectrum figure of HSA.
Fig. 9 is 3D fluorescence spectra of imidazole-2-carboxylic acid's nickel complex to BSA, HSA under different temperatures.A, c, e, g distinguish
When for different temperatures, the 3D fluorescence spectra of BSA, HSA；B, when d, f, h are different temperatures, the substance of complex and albumin
3D fluorescence spectra when amount is than being 20:1.
Specific embodiment
Specific embodiments of the present invention will be described in further detail with reference to embodiments.
The synthetic method of ligand 2- methylol -1H-4,5- imidazole-2-carboxylic acid of the invention is referring to paper Sheng-Run
Zheng,Song-Liang Cai,Mei Pan,Jun Fan,Tian-Tian Xiao,Wei-Guang Zhang,The
construction of coordination networks based on imidazole-based dicarboxylate
ligand containing hydroxymethyl group,CrystEngComm,2011,13,883–888。
The synthesis of 1 imidazole-2-carboxylic acid's nickel complex of embodiment
(1) it disperses 2- methylol -1H-4,5- imidazole-2-carboxylic acid in deionized water, is configured to 2- methylol -1H-4,
5- imidazole-2-carboxylic acid's concentration is the ligand solution of 0.05mol/L；
By Ni (NO3)2·6H2O is dissolved in deionized water, is configured to Ni (NO3)2·6H2O concentration is 0.05mol/L's
Nickel salt solution；
(2) by nickel salt solution and ligand solution according to 2- methylol -1H-4,5- imidazole-2-carboxylic acid and Ni (NO3)2·6H2O
The ratio of the mass ratio of the material 1:1 mixes；
(3) mixed liquor of step (2) is placed in polytetrafluoroethyllining lining stainless steel cauldron, it is anti-under the conditions of 120 DEG C
72h is answered, then room temperature is cooled to the rate of 5 DEG C/h, spontaneously dries, obtains blue prism-shaped crystal, as imidazole-2-carboxylic acid's nickel
Complex.
The structural characterization of 2 imidazole-2-carboxylic acid's nickel complex of embodiment
1, crystal structure analysis
Imidazole-2-carboxylic acid's nickel complex that embodiment 1 is obtained using Bruker APEX-II CCD type single crystal diffractometer into
The test of row crystal structure, test result are as follows:
The complex is monoclinic system, P2 (1)/c space group；Cell parameter
α=90 °, β=104.72 (3) °, γ=90 °；V=817.7A3；Z=4；Dc=1.880Mg/m3；R1=
0.0486, ω R2=0.1029.
Using graphite monochromatised Mo K alpha ray
Data are collected with ω scanning mode.Crystal structure
It is solved using direct method, and is extended with Fourier techniques, is modified by anisotropy, all data are through Lp factor correction.
SHELXL-97 program has carried out complete matrix least square method refine to all non-hydrogen atom coordinates and temperature factor.It obtains such as Fig. 1
The coordination context diagram of shown imidazole-2-carboxylic acid's nickel complex, the one-dimensional supermolecule of imidazole-2-carboxylic acid's nickel complex as shown in Figure 2
Chain structure figure, the Magnetic Properties of Three-Dimensional Supramolecular Complex net structure char of imidazole-2-carboxylic acid's nickel complex as shown in Figure 3.
As shown in Figure 1, the group of imidazole-2-carboxylic acid's nickel complex becomes [Ni0.5(H2hmIDC)(H2O)]n(n be greater than
Integer equal to 1, the interior composition for minimum asymmetric cell of bracket), molecular formula C6H6N2Ni0.5O6.The unit of complex
Structure includes the H of half of Ni (II) ion, deprotonation2hmIDC2-Anion and a water of coordination molecule.In complex
Ni (II) is hexa-coordinate, respectively and from two H2hmIDC2-Two oxygen atoms (O1, O1#1) on ligand, two nitrogen-atoms
Two oxygen atoms (O6, O6#1) chelating on (N1, N1#1) and two water of coordination molecule.Ni (II) is in the octahedron slightly distorted
NiN2O4In coordination configuration, O6, O6# 1 occupy octahedral vertex position, and bond angle O (6) #1-Ni (1)-O (6) is 180.00
(8)°.Ni-O coordination bond lengths around Ni (II) are Ni (1)-O (1):
Ni (1)-O (1) #1:
Ni (1)-O (6):
Ni (1)-O (6) #1:
Ni-N coordination bond lengths are Ni (1)-N
(1):
Ni (1)-N (1) #1:
As shown in Fig. 2, adjacent molecule connects into supermolecule chain structure by the O-H ... O between carboxyl.Oversubscription subchain is along b
Direction is connected by water of coordination molecule with O-H ... the O hydrogen bond on carboxyl, and two-dimensional structure is extended to.As shown in figure 3, oversubscription subchain
It accumulates to form supermolecule stereochemical structure by N-H ... the O hydrogen bond between imidazole ring and hydroxyl.
2, infrared spectrum analysis
Using the NICOLET iS50 Fourier transform infrared of Sai Mofei company, the U.S. (Thermo SCIENTIFIC) company
Spectrometer carries out examination of infrared spectrum (using KBr pressed disc method, at room temperature to imidazole-2-carboxylic acid's nickel complex that embodiment 1 obtains
Scanning, test scope 400-4000cm-1).Characteristic absorption peak (cm in infrared spectroscopy-1): 3309,2907,2791,1709,
1542,1456,1386,1269,1223,1096,1039,984,906,860,774,728,671,538,456.
3, X-ray powder diffraction is analyzed
X ' the Pert PRO type powder diffractometer produced using PANalytical company, is adopted by using 1 ray of Cu-K α
The diffraction data for imidazole-2-carboxylic acid's nickel complex that collection embodiment 1 obtains (see Fig. 4).
From Fig. 4 analysis it is found that the map and simulation map of the PXRD of the imidazole-2-carboxylic acid's nickel complex measured coincide substantially,
This illustrates that the purity of imidazole-2-carboxylic acid's class complex is very high, can be used for performance study.
3 imidazole-2-carboxylic acid's nickel complex of embodiment and sero-abluminous interaction
Laboratory apparatus: sepectrophotofluorometer model F7000, Hitachi, Japan production.
The preparation of reagent and test condition setting:
1, the preparation of sample liquid
2- methylol -1H-4,5- imidazole-2-carboxylic acid's nickel complex solution: 0.0046g 2- methylol -1H-4,5- miaow is weighed
It is 2 × 10 that azoles dicarboxylic acids nickel complex, which is configured to concentration,-3The DMSO solution of mol/L.
Tris-HCl buffer solution: Tris (trishydroxymethylaminomethane) 3.0285g, sodium chloride 7.3124g are taken, is transferred to
In 250mL volumetric flask, after distilled water constant volume, shake up.Then with salt acid for adjusting pH to 7.40.
Bovine serum albumin(BSA) (BSA) solution: weighing bovine serum albumin(BSA) 0.0333g, be placed in 10mL volumetric flask, is added
The dissolution of 5mL Tris-HCl buffer solution, with Tris-HCl solution constant volume, being configured to concentration is 5 × 10-5The ox blood of mol/L is pure
Protein solution.
Human serum albumins (HSA) solution: weighing human serum albumins 0.0331g, be placed in 10mL volumetric flask, is added
The dissolution of 5mL Tris-HCl buffer solution, with Tris-HCl solution constant volume, being configured to concentration is 5 × 10-5The human seralbumin of mol/L
Protein solution.
2, the setting of fluorescence spectrum test condition
Respectively under the conditions of 298K, 308K, excitation wavelength is set as 280nm, and exciting and emitting narrow peak is 5nm, 285
Its fluorescence spectrum of~450nm range scans；It is scanned within the scope of 250~550nm of launch wavelength, 200~400nm of excitation wavelength
3D fluorescence spectrum.And respectively in wavelength difference Δ λ=15nm and Δ λ=60nm, its synchronous fluorescent spectrum is scanned.
3, the measurement of fluorescence spectrum
Take 0.3mL bovine serum albumin solution (0.6mL human serum albumin solution), Tris-HCl buffer solution 14.7mL
(14.4mL) in a round bottom flask, being made into concentration is 1 × 10-6(concentration is 2 × 10 to the bovine serum albumin solution of mol/L- 6The human serum albumin solution of mol/L).The complex solution of different volumes is added, and measures its fluorescence light in different temperatures
Spectrum variation (with BSA interact when, complex concentration range: 0~8.47 × 10-4mol/L；When interacting with HSA, match
Conjunction object concentration range: 0~7.10 × 10-4mol/L)。
Fluorescence spectrum method for measuring complex and sero-abluminous interaction:
1, fluorescent quenching
The fluorescence of protein mostlys come from by trp residue, and the Intrinsic fluorescence of protein and its variation can be directly
Reflect the variation of trp residue itself and its local environment in protein.Using fluorescent spectrometry synthesized by embodiment 1
Complex studies the interaction of bovine serum albumin(BSA) (BSA), human serum albumins (HSA), as a result such as Fig. 5, BSA's
Concentration is 1 × 10-6Mol/L, with the increase of complex concentration, the Intrinsic fluorescence of BSA gradually weakens, when complex concentration is
8.47×10-4When mol/L, complex basically reaches balance to the quenching of BSA Intrinsic fluorescence；The concentration of HSA is 2 × 10- 6Mol/L, with the increase of complex concentration, the Intrinsic fluorescence of HSA gradually weakens, when complex concentration is 7.10 × 10- 4When mol/L, complex basically reaches balance to the quenching of HSA Intrinsic fluorescence.Illustrate at two temperature of this 298K, 308K,
The Intrinsic fluorescence of BSA, HSA can be quenched effectively by complex, and the shape of emission peak and position do not change, table
Form that fluorescence is weaker or non-blooming compound and causes BSA, HSA Intrinsic fluorescence between bright complex and BSA, HSA
It is quenched.
2, Quenching mechanism
There are static quenching and dynamic quenching in the reason of causing BSA, HSA fluorescent quenching.Dynamic quenching is a kind of energy transfer
Or the process of electronics transfer, the structure and physiological activity of protein are not influenced.Static quenching is led to since complex reaction has occurred
It is often to produce not fluorescent complex, influence can produce on Secondary structure, and its physiological activity may be influenced.
Dynamic quenching follows Stern-volmer equation:
F0/ F=1+Ksv[Q]=1+Kqτ0[Q] formula (1)
F0The fluorescence intensity of BSA, HSA when not respectively being added and be added quencher with F；KqFor bimolecular quenching process speed
Rate constant；KsvFor the quenching constant of Stern-volmer equation；τ0For large biological molecule average life span in the presence of no quencher,
About 10-8s；[Q] is the concentration of complex.
The rate constant K of BSA, HSA quenching process can be acquired by above formulaq(being shown in Table 1).
1 nickel complex of table and the rate constant of BSA, HSA interaction, binding constant, binding site number
Fig. 6 is under different temperatures, and imidazole-2-carboxylic acid's nickel complex schemes the Stern-volmer of BSA, HSA.It can by Fig. 6
Know, at different temperatures, good linear relationship is presented in complex-albumen Stern-volmer curve；With the liter of temperature
High Stern-volmer constant gradually decreases, and shows that complex is static quenching to the quenching mode of albumen.And at two temperature,
Complex is all larger than all kinds of quenchers to the maximum dynamic quenching of large biological molecule to the rate constant of the quenching process of protein
Rate constant 2.0 × 1010L·mol-1·s-1, it is not fluorescent multiple to further illustrate that complex is formd with protein-interacting
Close object.
3, binding constant and binding site number
Complex can be obtained with BSA, HSA binding constant to interact and binding site number by double-log equation:
log[(F0- F)/F]=logKb+ nlog [Q] formula (2)
Fig. 7 is log-log graph of imidazole-2-carboxylic acid's nickel complex to BSA, HSA under different temperatures.KbFor binding constant, n
For binding site number, calculated result (being shown in Table 1) shows that complex and BSA, HSA can form 1 binding site, illustrates complex
Stronger binding ability is all had with BSA, HSA.Using seralbumin as carrier, as drug 2- methylol -4,5- imidazoles two
Carboxylate nickel complex can pass through blood-borne and storage.
4, active force type
Active force between the large biological molecules such as drug and albumin mainly has intermolecular hydrogen bonding, Van der Waals force and electrostatic to draw
Power etc., the generation of intermolecular force can cause the variation of system thermodynamic parameter, by the change for measuring system thermodynamic parameter
Change the predominant intermolecular forces type that may determine that between drug and albumin.The binding force type of different pharmaceutical and albumin also not phase
Together, the determination of the active force type between drug and albumen can judge according to the two effect front and back enthalpy change Δ H and Entropy Changes Δ S,
When temperature change is little, the enthalpy change Δ H of reaction is regarded as constant.The active force type of complex and BSA, HSA are by Van ' t
The judgement of Hoff equation:
ln(K2/K1)=[1/T1-1/T2] Δ H/R formula (3)
Δ G=Δ H-T Δ S=-RTlnK formula (4)
R is gas constant (8.314472J K-1mol-1), K1、K2It is T for temperature1、T2When binding constant, nickel complex
Table 2 is listed in the thermodynamic parameter of BSA, HSA interaction.
The thermodynamic parameter of nickel complex and BSA, HSA interaction under 2 different temperatures of table
Under certain condition, the association reaction of drug and albumin whether can spontaneous progress and system gibbs free energy change
Related, when Gibbs free energy is less than zero, reaction spontaneous can be carried out.This spontaneous process can be divided into entropy driving and enthalpy drives
It is dynamic.Relationship such as table 3 between entropy, the size of enthalpy and active force type:
Relationship between the size and active force type of 3 entropy enthalpy of table
By table 2, table 3, the thermodynamic equilibrium constant Δ H < 0 of complex and BSA, HSA interaction, Δ S < 0 illustrate complex
There are hydrogen bond or Van der Waals forces between BSA, HSA.Δ G < 0 then shows that the interaction process of complex and BSA, HSA is
Spontaneous progress.
5, synchronous fluorescent spectrum
Emit stronger endogenous due to containing residues such as tryptophan, tyrosine and phenylalanines in seralbumin molecule
Fluorescence, wherein the fluorescence intensity of tryptophan and tyrosine is bigger, and the excitation spectrum of the two is similar, and emission spectrum can be serious
Overlapping, the mesh for selecting suitable Δ λ to can achieve simplified spectrum, reduce spectra overlapping and the bands of a spectrum that narrow using synchronous fluorescent spectrum
, and under normal conditions, the synchronous fluorescent spectrum of Δ λ=60nm only shows the characteristic spectrum of tryptophan, the synchronization of Δ λ=15nm
Spectrum only shows the characteristic spectrum of tyrosine.According to the variation of synchronous fluorescent spectrum launch wavelength can speculate complex to BSA,
The influence that HSA tryptophan and Tyrosine generate, and then may determine that the variation of protein conformation.
Fig. 8 is synchronous fluorescent spectrum figure of imidazole-2-carboxylic acid's nickel complex to BSA, HSA under different temperatures, emission maximum
The displacement result of wavelength is listed in table 4.As can be seen from Figure 8 with the increase of complex concentration, BSA, HSA when Δ λ=60nm
It is reduced more when maximum fluorescence intensity is than Δ λ=15nm, table 4 shows that the red shift of maximum emission wavelength when Δ λ=60nm is brighter
It is aobvious, it was demonstrated that as the conformation of addition BSA, HSA of complex change, the hydrophobicity of tryptophan local environment is reduced, i.e.,
Hydrophobic cavity configuration inside BSA, HSA is disintegrated, and the extension degree of peptide chain increased.
The displacement of 4 maximum emission wavelength of table
6,3D fluorescence spectrum
In three-dimensional fluorescence spectrum, the fluorescence intensity of fluorescent molecule had not only changed with excitation wavelength but also with variation in emission wavelength,
The variation of fluorescent molecule state can preferably be reflected by the finger print information and fluorescence peak position of three-dimensional fluorescence.It is three-dimensional glimmering
Light spectrum is capable of providing the details of protein conformation variation, the maximum emission wavelength and protein microenvironment of amino acid residue
Polarity have substantial connection.Imidazole-2-carboxylic acid's nickel complex is Rayleigh to three-dimensional spectrum such as Fig. 9, peak a (peak a) of BSA, HSA
Scattering peak, it is characterized in that λ ex=λ em (Δ λ=0)；Peak 1 (peak 1), peak 2 (peak 2) they are two kinds of typical spectrum peaks, from
The position at peak is seen: after complex is added, the Rayleigh scattering peak initial position of BSA, HSA and fluorescence peak position are without significant changes；
Be displaced from Stokes: after complex is added, the Stokes of BSA fluorescence peak is displaced constant, the Stokes at HSA fluorescence peak peak 2
Displacement is reduced；In terms of the intensity at peak: after complex is added, the enhanced strength of peak a, and the relative intensity of fluorescence peak has not
With the reduction of degree；In terms of fluorescence peak Strength Changes degree: the degree of 2 strength reduction of peak 1 and peak is different, it is clear that is matched
Object is closed to become apparent the quenching effect at peak 2.With the increase peak 1 of complex, 2 fluorescence intensity of peak reduction be due to complex with
The combination of albumin is located in the hydrophobic pocket being made of hydrophobic amino acid, and the introducing of exactly complex results in this hydrophobic micro-
The polar change of environment, and then cause the variation of BSA, HSA conformation.
The foregoing is merely the optimal embodiments of the present invention, and for those skilled in the art, the present invention can have
Various modifications and variations.All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on, should all
It is included within protection scope of the present invention.
Claims (6)
1. a kind of imidazole-2-carboxylic acid's nickel complex of 2- methylol -1H-4,5- imidazole-2-carboxylic acid preparation, which is characterized in that described
Imidazole-2-carboxylic acid's nickel complex molecular formula be C6H6N2Ni0.5O6。
2. imidazole-2-carboxylic acid's nickel complex according to claim 1, which is characterized in that cooperate imidazole-2-carboxylic acid's nickel
After object carries out crystal structure test, test result is as follows: the complex is monoclinic system, P2 (1)/c space group；Cell parameter
α=90 °, β=104.72 (3) °, γ=90 °；V=
817.7A3；Z=4；Dc=1.880Mg/m3；R1=0.0486, ω R2=0.1029.
3. a kind of preparation method of imidazole-2-carboxylic acid's nickel complex as claimed in claim 1 or 2, which is characterized in that including with
Lower step:
(1) it disperses 2- methylol -1H-4,5- imidazole-2-carboxylic acid in solvent, is configured to 2- methylol -1H-4,5- imidazoles two
Carboxylic acid concentration is the ligand solution of 0.05mol/L；
By Ni (NO3)2·6H2O is dissolved in solvent, is configured to Ni (NO3)2·6H2O concentration is the nickel salt solution of 0.05mol/L；
(2) by nickel salt solution and ligand solution according to 2- methylol -1H-4,5- imidazole-2-carboxylic acid and Ni (NO3)2·6H2O substance
Amount ratio 1:1 ratio mixing；
(3) mixed liquor of step (2) is placed in reaction vessel, reacts 72h, then under the conditions of 110-140 DEG C with the speed of 5 DEG C/h
Rate is cooled to room temperature, spontaneously dry to get.
4. the preparation method of imidazole-2-carboxylic acid's nickel complex according to claim 3, which is characterized in that the solvent is
Deionized water.
5. the preparation method of imidazole-2-carboxylic acid's nickel complex according to claim 3, which is characterized in that the reaction is held
Device is polytetrafluoroethyllining lining stainless steel cauldron.
6. the preparation method of imidazole-2-carboxylic acid's nickel complex according to claim 3, which is characterized in that the reaction temperature
Degree is 120 DEG C.
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